Herbicidal compositions and methods

ABSTRACT

Phytotoxic and soil sterilant compositions containing compounds of the formula (CH2 N-R)3(R1NCO)2 and having either of the following structures:   (3) MIXTURES OF (1) AND (2) WHEREIN R is alkyl having a maximum of four carbon atoms and R1 is selected from the group consisting of mono- and dihalosubstituted phenyl and monoitrosubstituted phenyl are disclosed as well as phytotoxic methods employing such compositions.

United States Patent n 1 Chapp Mar. 27, 1973 [54] HERBICIDALCOMPOSITIONS AND METHODS [75] Inventor: John P. Chapp, Kirkwood, Mo.

[73] Assignee: Monsanto Company, Saint Louis,

[22] Filed: Sept. 9, 1970 [21] Appl. No.: 70,892

Related U.S. Application Data [62] Division of Ser. No. 623,541, March16, 1967, Pat.

UNITED STATES PATENTS 3,525,747 8/1970 Jacobs ..71/92 X 3,126,404 3/1964Flynn et al... ....260/453 3,444,231 5/1969 Menz ..260/453 OTHER PUBLlCATlONS Lange; J. Am. Chem. Soc., Vol. 48, pp. 2,4402,444 (I926).

Primary Examiner-James 0. Thomas, Jr.

Clemens; J. Org. Chem., Vol.26, pp. 767-769 (1961).

Att0rneyNeal E. Willis, John J. Henschke, Jr. an David D; Centola [5 7]ABSTRACT Phytotoxic and soil sterilant compositions containing compoundsof the formula (Cl-l NR);,(RNCO) and having either of the followingstructures:

(3) mixtures 0f(1) and (2) wherein R is alkyl having a maximum of fourcarbon atoms and R is selected from the group consisting of monoanddihalo-substituted phenyl and monoitrosubstituted phenyl are disclosedas well as phytotoxic methods employing such compositions.

8 Claims, No Drawings HERBICIDAL COMPOSITIONS AND METHODS Thisapplication is a division of applicants application Ser. No. 623,541,filed Mar. 16, 1967, now U.S. Pat. No. 3,609,143.

Organic isocyanates are known to undergo addition and polymerizationreactions to yield a wide variety of products. The alcoholysis andaminonolysis of isocyanates to yield urethans and substituted ureas iswell known. The products are frequently solids and are used to identifythe corresponding alcohol or amine.

It has now been found that aryl is'ocyanates react with azomethines (ortheir trimers) to yield solid adducts which have phytotoxic activity.

it is an object of this invention to provide a novel process for thepreparation of isocyanate-azomethine adducts.

It is a further object of this invention to provide .a process for thepreparation of novel aryl isocyanateazomethine adducts.

It is a further object of this invention to :utilize isO-cyanate-azomethine adducts as herbicides.

Further objects, aspects and advantages of the invention will beapparent from the description "which follows.

Briefly, this invention provides a process for the preparation of novelisocyanate-azomethine adducts by reacting an azomethine (or its trimer)with an .aryl isocyanate in an approximate temperature range of50 C. Thereaction proceeds according to :the following equation:

3 cH,=,, ,,,+2R Nco (CH =R) (R.N.C.O) ,I wherein R is an alkyl grouphaving a maximum of four carbon atoms and R is selected from thegroupconsisting of halosubstituted phenyl and nitrosubstituted phenyl.

The term adduct as used herein is thechemical addition product formedfrom the reactants. It is .a ,new compound having a separate entity thanthe reactants. Therefore, the terms adduct" and compounds will be usedinterchangeably.

As seen in the equation above the molar ratio .of azomethine toisocyanate is preferably about 3:2. This ratio yields'an adduct (l)which is essentially uncontaminated with either of the startingcompounds. This optimum mole ratio was determined by infra-redandnuclear magnetic resonance studies of the reaction medium in whichvarious ratios of 'isocyanate and azomethine were reacted. The presenceof the NCO band at 4.5 micron (pi) in the infra-red wasindicative of thepresence of unreacted isocyanatein themedium. The presence of unreactiveazomethine appeared in the nuclear magnetic resonance spectra of :thereaction medium.

When two moles of azomethine per mole of isocyanate are reacted, thereaction medium was found, by the above analysis, to contain unreactedazomethine and the absence of any measurable amount .of unreactedisocyanate.

Changing the molar ratio of 1:1 shows by analysis that the isocyanate isin excess and that no'measurable amount of azomethine is present.

The reaction of3 moles of azomethine per 2'moles of isocyanate yieldedthe desired product without either unreacted isocyanate or unreactedazomethinebeing detected in the reaction medium. This, therefore,

shows that the adducts consist of 3 moles of azomethine per 2 moles ofisocyanate. This was confirmed by infra-red, nuclear magnetic resonance,molecular weight and elemental analysis of the adduct.

It is apparent from the above description that some adduct is formedregardless of the proportions of reactants used in the process. In orderto minimize the requirements of separation of the desired adduct fromthe reaction mixture, it is preferred to use an approximate molar ratioof 3:2 (azomethinezisocyanate).

In the preparation of the adducts, the reactants are normally dissolvedin an organic solvent, such as pentane, and combined, preferably attemperatures in the approximate range of 0".-50 C. The reaction mixtureis then maintained for an extended period of time, about 2 .to 4 days,at approximately room temperature. The

product, which separates from the solvent as a solid, is

separated and triturated with a suitable solvent, e.g. diethyl ether,and the solvent removed, preferably under reduced pressure atapproximately room temperature.

Other solvents, such as aliphatic and aromatic hydrocarbons, ethers andthe like, can be used as the reaction medium. These solvents include,but are not limited to, pentane, hexane, heptane, benzene,

.cyclohexane, toluene, methyl ethyl ether, diethyl ether,

and ,isopropyl ether. Preferred solvents are those in which the adductis insoluble, both the azomethine and isocyanate. are soluble, and whichcan be easily removed .under reduced pressure at about room tem-:peratures. Aromatic hydrocarbons can be used, but since they usuallyhave a high solubility for the product and are difficult to remove fromthe product, aliphatic hydrocarbons are generally preferred as thereaction .medium.

| o j dlfi x'- N-R wherein X and X 'is either R or R and Y and Y" iseither H or oxygen; R and R are as previously defined; provided thatwhen X is R, then X is R, Y is H and Y .isoxygen (compound Ill); andfurther provided that when X is R, then X is R; Y is oxygen and Y is H(compound IV).

This configuration is based on infra-red, nuclear magnetic resonance,molecular weight, physical properties, elemental analysis andexperimental reaction data.

The adduct formedby the process of this invention is either compoundIll, compound IV or a mixture of the two compounds:

These compounds, 111 and IV differ in the position of lo the isocyanategroups, which are adjacent groups in formula IV and separated by anazomethine group in formula 111. Both formulas 111 and IV satisfy themolecular weight and spectral data. Nuclear magnetic resonance data showthat all N-methyl groups and methylene groups are non-equivalent, whichwould be expected from both formulas.

Preparation of the reactants azomethines and isocyanates are accordingto well-known synthetic procedures. Azomethine trimer(hexahydrotriazine) was prepared by reacting an aldehyde and an amineaccording to the procedure of H. Ulrich and .l. Rubenfeld, Journal ofOrganic Chemistry 26, 1937 (1961).

The following examples are illustrative only of the invention, thepreparation of the compounds and their use as herbicides and soilsterilants, and should not be construed as limiting the invention. Forconvenience and clarity, the nomenclature used in the examples andthroughout the specification is based on the structure of formula lll.

EXAMPLE 1 Preparation of l,5-Bis-(3,4-dichlorophenyl)-hexahydro-3,7,9-triethyll ,3,4,7,9-pentazecine-2,6-(l l-l,5H)-dione is according tothe following procedure:

Trimeric N-ethyl azomethine (1,3,5-triethylhexahydro-triazine) (0.0367mole, 6.27 g) was dissolved in about 50 ml dry pentane and then added,with stirring, to a clear filtered solution of 0.0734 mole (13.8 g) of3,4-dichlorophenylisocyanate dissolved in about 100 ml of dry pentane.An exothermic reaction occurred upon addition of the azomethine.Following the addition the reaction flask was sealed and allowed tostand at room temperature (about C.) for 2 days. The pentane solutionwas then decanted and the residue pulverized to a fine white powder,yield 16.2 g. This powder was then triturated with about 50 ml drydiethyl ether, the ether removed and the residue vacuum stripped ofsolvent at room temperatures to yield 13.3 g of a dry white solid, m.p.l09-l 12.5 C. (decomposition), c,,H,,c1,N,o,:

Analysis Calculated Found N 12.80 12.57 Cl 25.91 25.94 M.W. 547 538Molecular weight determination was an osometric determination inchloroform. Infra-red spectra had a strong carbonyl bond at 6.0 6.1 u.Nuclear magnetic resonance spectra were in CDCl and provided thefollowing results:

NCH N NCH,CH, NCH CH, (Sing1et,2H ea.) (Quartet,2H ea.) (Triplet.3H ea.)4.02 2.70 1.08

EXAMPLE 2 The procedure of Example 1 was repeated, with the exceptionthat dry diethyl ether was used as the solvent in place of dry pentane,to yield l,5-Bis(3,4- dichlorophenyl) hexahydro-3,7,9-triethyl-1,3,5,7,9- pentazecine-2,6-( 1H,5H )-dione.

EXAMPLE 3 The procedure of Example 1 was repeated using trimericN-methyl azomethine (1,3,5-trimethyl hexahydrotriazine) in place of thetrimeric N-ethyl azomethine, to yield1,5-Bis(3,4-dichlorophenyl)hexahydro-3,7,9-trimethyl-1,3,5,7,9-pentazine-2,6-(lH,5H)-dione, C l-l CI N O m.p. l0l112 C. (decomposition). Analysis:Calculated: N 13.87; C1 28.08 M.W. 505; Found: N 13.33; C1 27.58; M.W.512. Molecular Weight determination was an Osometric determination inbenzene.

EXAMPLE 4 The procedure of Example 1 was repeated using 4-nitrophenylisocyanate in place of 3,4-dichlorophenylisocyanate to yield1,5-Bis(4-nitrophenyl)-hexahydro-3,7,9-triethyl-1,3 ,5,7,9-pentazecine-2,6-(l H,5H)-dione.

EXAMPLE 5 The procedure of Example 1 was repeated using 3-chloro-phenylisocyanate in place of 3,4-dichlorophenylisocyanate toyield l,5-Bis(3-chlorophenyl)hexahydro-3 ,7,9-triethyl-1,3,5,7,9-pentazecine-2,6-(1 H,5H)-dione, c n ci mo m.p. 97104 C.(decomposition). Analysis: Calculated: N 16.06, C1 16.26; M.W. 436;Found: N 15.84, C1 16.20; M.W. 436. Molecular weight determination wasan osometric determination in chloroform.

The compounds of this invention have been found to exhibit soilsterilant and herbicidal activity. Herbicidal activity has been shown inboth the pre-emergent and post-emergent state, that is, the applicationof an effective amount of the compounds of this invention to seeds,emerging seedlings, the roots or above ground portion of establishedvegetation, controls or modifies the growth of, germinated seeds,emerging seedlings and established vegetation.

The active ingredient can be applied alone or in combination with amaterial referred to in the art as a herbicidal adjuvant in liquid orsolid form. The herbicidal compositions of this invention are preparedby admixing the active ingredients with an adjuvant which includesdiluents, solid or liquid extenders, carriers and conditioning agents toprovide compositions in the form of finely divided particulate solids,granules, pellets, solutions and aqueous dispersions or emulsions. Thusthe active ingredient can be used with an adjuvant such as afinely-divided particulate solid, a solvent liquid of organic origin,water, a wetting agent, dispersing agent, an emulsifying agent or anysuitable combination of these.

Herbicidal composition as used herein and in the appended claimsincludes not only compositions in a suitable form for application butalso concentrated compositions which require dilution or extension witha suitable quantity of liquid or solid adjuvant prior to apingredientper acre has been applied to the soil surface. plication. The pans arewatered through apertures in the bottom The following examplesillustrate the herbicidal acof the pans, and are then maintained underordinary tivity of the adduct: greenhouse conditions of sunlight andwater for 14 5 days.

EXAMPLE 6 The plants are observed at the end of 14 days and the PoStEmergent Herbicidal Activity results recorded. The herbicidal activityindex is based v on the average percent germination ofeach seed lot. Analuminum pan approxima ly 9 X 13 X 2 Inches 15 The pre-emergentherbicidal activity index used in filled with top soil and the soilcompacted to within T bl [I i defin d as follow three-eights inch fromthe top of the pan. A predetermined number of seeds of the followingplant species:

cotton soybeans cocklebur crab grass, Average Percent NumericalHerbicidal lambsquarter, wild oats, smartweed, brome, barnyardGermination Scale Activity grass, sugar beet, wheat, rice andcoffeeweed, are

placed on the top of the soil and the pans filledwith top 76 to 100 0 NActivity soil and leveled. The pans are watered through apergig Z3 i 'gggf 'lg ,tures in the bottom of the pans and are then maintained 0 to 3Severe Activity under ordinary greenhouse conditions of sunlight andwater for 14 days.

' The ingredient to be tested is applied to the 14 day old Plants in p yform- The herbicidal p y a I Identification of the seeds used is asfollows: acetone-water solutions containing 0.1 and 0.02 percent byweight of active ingredient and 0.4 ml of a 3:]

A Morning Glory H Crab Grass cyclohexanol emulsifier (butyl-amine saltof dodecyl- B wild Oat l Pigweed C Brome J Soybean benzenesulfomc acid35 percent, tall 011 ethylene D Rye Grass K wild Buckwheat oxidecondensate 65 percent) solution and are applied 5 Radish L Tomato at arate of 2 and 0.4 pounds of active ingredient per g 21%;? M

acre of land, respectively. The treated plants are placed in agreenhouse and the effects are observed and recorded after 28 days. L

The results are tabulated, as percent control, in

Table 1. Identification of the plants used is as follows:

The compound identification is the same as in Table TABLEII.-PREEMERGENT HERBICIDAL ACTIVITY A Cotton H Smartweed Raw! 3 l Bmme(ass Compound A n c 1) E F G H I J K L M C Soybean K Barnyard Grass DCocklebur L SugarBeet (l) 10 2 3 2 3 2 3 3 3 3 0 3 3 3 E CrabGrass MWheat (2) 10 3 3 3 3 3 3 3 3 3 2 3 3 3 F Lambsqumr 0 Rice 8%:1111113: 13i 1 i i 3 i 3 3 3 2 3 i G Wild Oat P CoffeeWeed TABLE I.POSTEMERGENTHERBICIDAL ACTIVITY Rate, Compound lbs/acre A B C D E F G H I J K L M N0 I (I) 2 0 60 100 100 35 100 10 30 15 100 I 15 100 30 40 90 0.4 0 0 0 010 100 0 0 0 100 0 60 0 5 0 15 2) 2 10 25 -0 l0 0 '55 0 15 0 25 0 0 5 2010 25 0.4 o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3) 2 0 0 0 0 25 90 0 15 0 60 030 0 5 0 0 0.4 0 0 0 o 0 0 0 0 0 0 o 15 0 0 0 0 (4) 2 10 25 10 40 25 10060 10 95 35 75 15 15 15 58 0.4 0 0 0 0 0 60 0 0 0 100 0 30 0 0 0 l0 (1)1,5-bls(flA-dlchlorophenyb)hexbhydro-(iJfl-trlmethyl-l,3,5,7,9-pentazecine-2,6-(1H,5II)dione. (2) 1,5-bls(3-chlorophenyl-)hexahydroQJfi-trirnethyl-l,3,5,7,9-pentazeclne-2,6-(1H5H) dlone. (3) 1,5-bls(3,4-dichlorophenyl-)hexahydro-3,7,9-trlethyl-1,3,5,7,9-pentazeclne-2,6-(1,5H) dlone. (4)1,5-s(4-chor0phenyl-)hexhhydro$,7,9-trlmethyl-1,3,5,7,9-pentaieclne-g(i-(lILQH) dione. H

EXAMPLE 7 At concentrations less than 5 pounds per acre, and

preferably in the approximate range of 2 to 4 pounds Pre'emergemHerbmdaAct'v'ty per acre, the compounds of this invention exhibit a Analuminum pan approximately 9 X 6 X 3 inches, is Selective pre-emergentherbicidal effect in addition to filled with a good grade of top soiland the soil comthe residual effect which is advantageous for specificpacted to within three-eighths inch from the top of the weed control incrops Such as corn, cotton d s y a pan. A predetermined number of seedsof the following (Tablii plant species: morning glory, wild oat, brome,rye grass,

radish, sugar beet, foxtail, crab grass, pigweed,

soybean, wild buckwheat, tomato and sorghum are An aluminum pan,approximately 9 X 6 X 3 inches is placed on the top of the soil and thepans filled with top filled with a good grade of top soil and the soilcomsoil and leveled. The herbicidal composition is applied pacted towithin three-eighths inch from the top of the by spraying the surface ofthe top layer of soil, prior to pan. A predetermined number of seeds ofthe species watering the seeds, until a rate of 10 pounds of activelisted in Table Ill are placed on the top of the soil and EXAMPLE 8 Theplants are observed at the end of 14 days or 28 days depending upon therate of herbicidal application and the results recorded. The herbicidalactivity index is based on the average percent germination of each seedlot, as described in Example 7.

Identification of the seeds used is as follows:

of the pan and then maintained under normal greenhouse conditions, usingsubirrigation, for a period of 6 weeks. At the end of this period, theplants are observed for the effect of the active ingredients.

The pans will then be oven dried, the top one-half inch of the topsoilremoved and the plants reseeded. The removed topsoil is mixed with theequivalent of 50 pounds per acre of nitrogen and the topsoil replaced.The pans are then watered, as before and maintained under normalgreenhouse conditions, with subirrigation, for 6 weeks. At the end ofthis period, the plants are once again observed for the effects of theactive ingradient.

The second cycle is repeated as long as three or more IS A gotten gfgrasses or broadleafs or the nutsedge are controlled 75 B orn igwee CSoybean K Barnyard Grass percent or more by the or ginal application. DCocklebur L Sugar Beet The soil sterilant activity IS reported m TableIII as E crabbol'ass v l L f percent control. The compound used in TableIV is the g gri 0 is ea adduct of 3,4-dichlorophenylisocyanate and N- HSmartweed P Coffee Weed methylazomethine.

TABLE lIL-PRE-EMERGEN'I HEBBICIDAL Ao'rivfii? Plants Rate, observedCompound lbs/acre A B (J D E F G ll 1 J K L M N 0 l ulter Remarks 4 0 00.5 1.5 3 3 2 2.6 2 3 3 3 1.5 2.6 06 3 14days.-.Averageof2runs. 1 2 0 00 0 2 3 0 0 0 3 2 2 0 0 1 2 28days D0.

1 0 0 2 3 0 0 0 a 0 3 1 0 0 0 ...do....

(1) Adduet 0f 3,4-dlch]oroplienyllsoeyanate and N-methylazomethlne.

Many herbicides are deficient in that they are rapidly TABLE IVdissipated or destroyed in the soil and, therefore, have 30 SOISTERILANT AC little or no residual effect.

When such compounds are used for weed control in Cycles crops, multipleapplications are required during the l l 2 3 4 d h t. d t d t Prgweed100 100 100 100 crop growing an arves mg perio s omsurea equa eMrningG|my(Ann 95 95 90 20 weed control. Smartweed 100 100 85 30Cockelbur I00 75 For applications requiring a soil sterilant effect,such Italian Rye Grass 100 I00 I00 90 as railroad right away where plantcontrol over an ex- Rye 60 100 [00 6Q tended period of time of severalyears is desired, these Sorghum 99 100 75 60 th d I fSO Quackgrass I00100 90 I00 prior ar er ici es are app re m arge quan I res o Numedge(No') 0 0 0 40 to 60 pounds per acre.

It has been found that the compounds of this invention possess aresidual effect when applied in relatively small amounts of 5 to 10pounds per acre. This persistency permits the use of the compounds assoil sterilants for general weed control.

At concentrations less than 5 pounds per acre, and preferably in theapproximate range of 2 to 4 pounds per acre, the compounds of thisinvention exhibit a selective pre-emergent herbicidal effect which maybe advantageously used for specific weed control in crops such as corn,cotton and soybean.

An example of the soil sterilant activity of the compounds of thisinvention for general weed control is illustrated by the following:

EXAMPLE 9 Metal pans, 9 A X 5 95 X 2 =34 inches, are filled, andcompacted, to the top with air dry Memphis silt loam. The activeingredient is sprayed on the soil surface until a rate of 5 pounds peracre has been applied to the soil surface. The pans are then held dryfor 3 weeks under greenhouse conditions. After the 3 week period, thetop one-half inch of soil is removed and the appropriate plant speciesto be tested seeded. The top soil, which was removed, is mixed by handand replaced over the seeds. The pans are then watered through thebottom Results are in per cent control.

Active ingredient adduct of 3,4-dichlorophenylisocyanate andN-methylazomethine applied to a rate of 5 pounds per acre.

From the foregoing data, it is apparent that the compounds of thisinvention are effective as soil sterilants and as preand post-emergentherbicides.

Selective preand post-emergent herbicidal activity was obtained byapplications of amounts as low as 1 lb. ofa compound of this inventionper acre.

Soil sterilant activity has been shown when applied at a rate equivalentto 5 pounds per acre. In normal application a rate equivalent to 5-50pounds per acre is used.

ln order that the active ingredients of this invention can be used totheir greatest advantage in modifying the growth of plant systems insoil, preferred herbicidal compositions have been developed whichcomprises certain wettable powders, aqueous suspensions, dustformulations, granules, emulsifiable oils and solutions in solvents.These compositions can also contain, as a conditioning agent, one ormore surface active agent in an amount sufficient to render a givencomposition containing the active component readily dispersible in wateror in oil. The term surface-active agent" includes wetting agents,dispersing agents, suspending agents, emulsifying agents and the like.

Surface-active agents which-can be used in the herbicidal compositionsare set out, for example, in Searle U.S. Pat. No. 2,426,417; Todd U.S.Pat. No. 2,655,447;

' Jones U.S. Pat. No. 2,412,510; or Lenher U.S. Pat. No.

2,139,376. A detailed list of such agents is set forth in Detergents andEmulsifiers Up-to-date (I961) by J. W. McCutcheon, Inc.; Bulletin E-607of the Bureau of Entomology and- Plant Quarantine of the U.S. Departmentof Agriculture; and Soap and Chemical Specialties (November 1947) pages8,0l1 et seq. The surface-active agents are generally employed atconcentrations of about 1 to 15 parts by weight per 100 parts by weightof the herbicidal composition.

Powdered or dust herbicidal compositions are usually characterized bytheir free-flowing and rapid settling properties. They are dense,finely-divided particulate compositions intended for application to the.

soil in a dry form. Dusts are primarily comprised of the activeingredient and a dense, free-flowing, finely divided particulateextender. For ease and convenience in manufacture, an inert absorptivegrinding aid, such natural clays, diatomaceous earth, synthetic mineralsderived from silica, and the like may be used. Preferred grinding aidsinclude, but is not limited to, attapulgite clay, diatomaceous earth,synthetic fine silica, synthetic calcium silicate and syntheticmagnesium silicates. Wetting agents, as hereinafter described can alsobe incorporated in the dust composition.

The inert solid extenders, for use in dusts, are of vegetable andmineral origin and possess relatively low surface areas and poor liquidabsorption. Extenders used include, but is not limited to, micaceoustalcs, il-

. litic clay, pyrophyllite, dense kaolin clays, ground calciumphosphate, rock dust and tobacco dust.

Dusts usually contain from about 0.5 to 99 parts active ingredient, O to50 parts grinding aid, to 3 parts wetting agent and 1 to 99.5 partsdense solid extender, all parts being by weight based on the totalweight of the dust.

Wettable powder herbicidal compositions are similar to the powder ordust composition. A wettable herbicidal powder is a water-dispersiblecomposition containing one or more active ingredients, an inert solidextender and one or more wetting and dispersing agents.

The preferred wetting agent includes alkyl benzene sulfonates, alkylnaphthalene sulfonate, sulfated fatty alcohols, sulfated fatty amines orsulfated fatty acid amides, long chain acid'esters of sodiumisothionate,

esters of sodium sulfosuccinate', sulfated or sulfonated fatty acidesters, petroleum sulfonates, sulfonated vegetable oils, ditertiaryacetylinic glycols and the like. Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium liquor sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonates, polymethylenebis-naphthalenesulfonate and sodium N-m ethyl-N-(long chain acid)taurates.

Inert solid extenders for use in wettable powder comingredient, fromabout 0.25 to about 3.0 parts of wetting agent, from about 0.25 to about7 parts of dispersant and from about 4.5 to about 94.5 parts of inertsolid extender, all parts being by weight of the total composition. Acorrosion inhibitor and/or antifoaming agent may be substituted, whereneeded, for

by'weight of the solid inert excoverage.

Emulsifiable oils are usually solutions of the active ingredient inwater-immiscible solvents together with a surfactant. The compositiongenerally contains from about 5 to 95 parts active ingredient, about 1to 10 parts surfactant and about 4 to 94 parts solvent, all

parts being by weight based on the total weight of the A composition.Solvents which are used in this composition includes, but is not limitedto, hydrocarbons and -water immiscible ethers, esters, ketones and thelike.

The surfactant may be anionic, cationic or non-ionic and includes alkylaryl polyethoxy alcohols, alkyl and alkyl aryl polyether alcohols,polyethylene sorbitol or sorbitan fattyacid esters, polyethylene glycolfatty esters, amine salts of fatty alcohol sulfates, long chain alcoholsand oil solublepetroleum sulfonates or mixtures thereof.

Granules are physically stable particulate compositions comprising anactive ingredient adhering to or distributed through a basic matrix ofan inert, finely-divided particulate extender. Preferred extenders arethe porous, absorptive, preformed particles such as the pro-formed andscreened particulate, and the finely-divided clays such as kaolin clays,hydrated attapulgite, illitic clay or bentonitic clays. These extendersare blended or sprayed with the active ingredient to form the granules.The mineral particles are usually in the size range of 10 to 100 mesh,with 14 to 80 mesh being preferred and 20 to 40 mesh being the optimumsize desired.

Granular compositions are comprised of about 0.05 to 30 parts by weightof active component per 1 part by weight of clay and about 0 to 0.05parts by weight of wetting agent per l part by weight of clay.

' ypropylamino)-6-methylthio-s-triazine,

positions are usually of mineral origin such as the natu- The herbicidaland soil sterilant composition of this invention can include otheradditaments, such as, fertilizers, other phytotoxicants, pesticides andthe like, used as adjuvants or in combination with any of theabove-described adjuvants.

Phytotoxicants useful in combination with and as synergistic mixtureswith the compounds of this invention include 2,4-dichlorophenoxyaceticacid, 2,4,5- trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetieaeid and their salts, esters and amides; triazinederivatives, such as 2,4-bis(3-methox- 2-chloro-4-ethyl-amino-6-isopropylamino-s-triazine and 2-ethylamino-4-isopropyl-amino-o-methylmercapto-striazine; ureaderivatives, such as 3-(3,4-dichlorophenyl)-l,l-dimethyl urea and3-(p-chlorophenyl)-l,ldimethyl urea, 3-(3,4-dichlorophenyl)-l-methyl-l-'methoxy urea; acetanilides such as N-isopropyl-achloroacetanilide,N-ethyl-a-chloro-Z-methylacetanilide and 2-t-butyl-2"-chloro-6-methylacetanilide; acetamides, such as N,N-diallyl-a-chloro-acetamide,N-(a-chloroacetyl) hexamethylene imine, N,N-diethyla-bromoacetamide andthe like.

The compounds of this invention can be applied to the soil or plantsystem in any convenient fashion, such as mixing with the media, byapplying to the surface of the soil in dry form and thereafter draggingor discing into the soil to the desired depth, by employing a liquidcarrier to carry the ingredient into the soil, and the like. Applicationto plants can be by any of the conventional methods, such as powderdusters, boom and hand sprayers, spray clusters and the like.

The desired rate of application is as previously recited, however,quantities outside this range can be used. Optimum application rate isdependent upon, among others, soil texture, desired depth of ingredientin the soil, and the specific use for which applied, such as preorpost-herbicidal activity or soil sterilant. in soil applications, it isdesirable that the active ingredients be distributed to a'depth of atleast 0.2 inches. One skilled in the art can readily determine from thisspecification, including examples, the application rate for any specificsituation.

While the illustrative embodiments of this invention have been describedhereinbefore with particularity, it

will be understood that various other modifications will be apparent toand can readily be made by those skilled in the art without departingfrom the scope and spirit of the invention. Accordingly, it is notintended that the I scope of the claims appended hereto be limited tothe examples and description set forth herein but rather the claims beconstrued as encompassing all the features of patentable novelty whichreside in the present invention including all features which would betreated as equivalents thereof by those skilled in the art to which theinvention pertains.

What is claimed is:

l. A herbicidal composition comprising a herbicidally effective amountof a compound of the formula (Cl"l -=-NR);,(RNCO) and selected from thegroup consisting of wherein R is alkyl having a maximum of four carbonatoms and R is selected from the group consisting ofmononitro-substituted phenyl and monoor dichlorosubstituted phenyl.

2. A herbicidal composition in accordance with claim I, in which R ismethyl and R' is monoor dichlorophenyl.

3. A herbicidal composition in accordance with claim 2, in which R is3,4-dichlorophenyl.

4. A herbicidal composition in accordance with claim 2, in which R is4-chlorophenyl.

5. A method for the control of vegetation which comprises applying to alocus to be protected a herbicidal composition comprising a herbicidallyeffective amount of a compound of the formula (CH ==N R);,(R'NCO) andselected from the group consisting of wherein R is alkyl having amaximum of four carbon atoms and R' is selected from the groupconsisting of mononitro-substituted phenyl and monoordichlorosubstituted phenyl.

6. A method for the control of vegetation in accordance with claim 5, inwhich R is methyl and R is monoor dichlorophenyl.

7. A method for'the control of vegetation in accordance with claim 6, inwhich R is 3,4-dichlorophenyl.

8. A method for the control of vegetation in accordance with claim 6, inwhich R is 4-chlorophenyl.

T I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,723,087 Datea March 1973 Inventor(s) JOhh Paul Chup It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

On the cover page of the patent, the inventor's name which reads as"John P. Chapp," should read' John P; Chupp,

I A Column 1, line 52 which reads as- 5(CH 2 R Nco (CH2=R)3 (R1NCO)2should read Signed and sealed this 18th day' of June 1974.

(SEAL) Attest: v I EDWARD M.FLETCHER,JR. C. MARSHALL DANN AttestingOfficer Commissioner of Patents FORM P0405) H0459) Q v I USCOMM-DCscan-ps9 t U.$. G OVERNHE NT PRINTING OFFICE 2 I98! O -365 -33l

2. A herbicidal composition in accordance with claim 1, in which R ismethyl and R1 is mono- or dichlorophenyl.
 3. A herbicidal composition inaccordance with claim 2, in which R'' is 3,4-dichlorophenyl.
 4. Aherbicidal composition in accordance with claim 2, in which R'' is4-chlorophenyl.
 5. A method for the control of vegetation whichcomprises applying to a locus to be protected a herbicidal compositioncomprising a herbicidally effective amount of a compound of the formula(CH2 N-R)3(R1NCO)2 and selected from the group consisting of
 6. A methodfor the control of vegetation in accordance with claim 5, in which R ismethyl and R1 is mono- or dichlorophenyl.
 7. A method for the control ofvegetation in accordance with claim 6, in which R'' is3,4-dichlorophenyl.
 8. A method for the control of vegetation inaccordance with claim 6, in which R'' is 4-chlorophenyl.